Sunscreen compositions with improved water resistance of uva sunscreen active agents

ABSTRACT

Sunscreen compositions, products and methods that include at least one UVA sunscreen active agent, at least one UVB sunscreen active agent, and one or more water insoluble film forming polymers. The compositions, products and methods may further include one or more active or inactive cosmetic ingredients. The water insoluble film forming polymers synergistically affect the UVA and UVB sunscreen active agents, in particularly the UVA sunscreen active agents by significantly enhancing the water resistance of the UVA sunscreen active agents after water exposure as determined by the SPF and UVAPF values measured before and after water exposure.

The present application is a continuation of U.S. patent applicationSer. No. 15/264,003, filed Sep. 13, 2016, which claims priority to U.S.Provisional Application No. 62/218,032, filed Sep. 14, 2015. Allapplications noted above are hereby incorporated by reference in theirentirety.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The invention is directed to sunscreen compositions, and in particular,sunscreen compositions, products and methods having polymeric additivesthat improve water resistance of UVA actives contained therein.

2. Description of Related Art

Numerous sunscreens are currently available for protecting keratinoussubstrates such as skin and hair from ultraviolet (UV) solar radiationfalling within both the UVB region (between 290 nm to 320 nmwavelengths) and the UVA region (between 320 nm and 400 nm wavelengths).Protection from UVA radiation is measured as a Protection Factor—UVA orPFA. Protection from UVB radiation is measured as a Sun ProtectionFactor or SPF. For instance, UVB radiation is absorbed by the epidermislayer causing erythema and cellular mutations, all of which damage theskin and underlying tissue. UVA radiation is even more damaging as itreaches deeper into the dermis layer. As such, UVA radiation maysuppress immune functions, lead to loss of skin elasticity, promotepremature signs of aging, as well as other undesirable health effects.

Currently available sunscreens can protect against both UVB and UVAradiation. However, water exposure and other adverse conditions such assweat, can lead to diminished protection as the sunscreen can wash offthe skin. Sunscreen manufacturers provide the consumer with a waterresistance rating that is dictated by the 2011 U.S. Food & DrugAdministration (FDA) Final Rule for Water Resistance wherein a sunscreencomposition must meet the critical wavelength of 370 nm. However, thecritical wavelength protocol does not take into account the efficacy ofthe sunscreen composition after exposure to real life conditions ofwater, sweat, salt water or pool water. Under the adverse conditions ofwater, salt, and/or chemicals, the sunscreen composition can lose itsefficacy and provide limited or no protection to the consumer. Yet eventhough the critical wavelength is met, SPF is primarily a measure ofprotection against UVB radiation only. As such, a loss in protectionagainst UVA radiation after a period of water immersion is not accountedfor in efficacy testing.

The SPF of a sunscreen composition is determined by measuring theminimal erythema response on human skin treated with a sunscreencomposition and untreated human skin on a single human subject. Fromthese two measurements, the SPF is the ratio of the energy required togenerate erythema on treated skin as compared to the energy required togenerate erythema on untreated skin. While erythema is produced on humanskin exposed to both UVB and UVA rays, UVB rays play a much greater rolein their effect on skin. The erythemal action spectrum reveals that 99%of erythemal action resides in the UVB region and only 1% in the UVAregion.

The marker used to measure UVA Protection Factor (UVAPF) is referred toas Persistent Pigment Darkening (PPD), which implements use of UVA raysonly. PPD is based on the skin's response to the amount of UVA thatenters the viable epidermis. One such test measures sunscreen-protectedPPD skin to the unprotected PPD skin after exposure to UVA. However,these tests do not measure water resistance of UVA sunscreens.

Again, whether or not a sunscreen is deemed water resistant is based onthe 2011 FDA Final Rule for water resistance. By relying on testing inwhich 99% of the effective energy dosage comes from UVB rays, and only1% coming from UVA rays, currently available sunscreens incorrectlyimply that both UVB and UVA protectants are “water resistant” to thesame degree. As such, loss in protection against UVA radiation after aperiod of water immersion is not accounted for in sunscreens.

To overcome these deficiencies in the prior art, the present inventionprovides products, methods and sunscreen compositions with an increasein water resistance, namely, an increase in the water resistance of theUVA sunscreen active agents.

SUMMARY OF THE INVENTION

Bearing in mind the problems and deficiencies of the prior art, it istherefore an object of the present invention to provide sunscreencompositions, products, and methods thereof having broad spectrum ofwater resistance protection across both the UVB and UVA bands of the UVspectrum.

It is another object of the present invention to provide a sunscreencomposition comprising: one or more UVA sunscreen active agents; one ormore water insoluble film forming polymers, wherein the one or morewater insoluble film forming polymers increase water resistance of theone or more UVA sunscreen active agents such that the level of retentionof UVAPF values after water exposure, as determined by UVAPF valuesmeasured before and after water exposure, is greater than at least 60%,preferably greater than at least 70%, and most preferably greater thanat least 80%.

The one or more UVA sunscreen active agents may comprise avobenzone;terephthalylidene dicamphor sulfonic acid; bis-disulizole disodium;disodium phenyl dibenzimidazole tetrasulfonate; diethylaminohydroxybenzoyl hexylbenzoate; bis-diethylamino hydroxybenzoyl benzoate;bis-benzoxazolylphenyl ethylhexylamino triazine, or combinationsthereof. The sunscreen composition may further include one or more UVBsunscreen active agents comprising octocrylene; octinoxate; octisalate;homosalate; ensulizole; ethylhexyl triazone; enzacamene; amiloxate;diethylhexyl butamido triazine; benzylidene malonate polysiloxane;padimate-O; trolamine salicylate; cinoxate; p-aminobenzoic acid andderivatives thereof; or combinations thereof. The sunscreen compositionmay also include one or more sunscreen active agents that absorb bothUVA and UVB radiation such as, for example, oxybenzone; meradimate;titanium dioxide; zinc oxide; bis-octrizole; bemotrizinol; drometrizoletrisiloxane; sulisobenzone; dioxybenzone; or combinations thereof.

The one or more water insoluble film forming polymers may comprisemonomers, copolymers, cross polymers and terpolymers of organo-siliconehybrids, biopolymers, acrylate, abietic acid derivatives, polyolefins,silicone resins, vinyl acetates, maleates, alkyl esters, long chain andshort chain carboxylic acids, or combinations thereof. The one or morewater insoluble film forming polymers may be present in a non-aqueoussolvent. The non-aqueous solvent may comprise an alcohol, ether, fattyacid, silicone fluid, ester, hydrocarbon, fluorinated hydrocarbon, orcombinations thereof. The one or more water insoluble film formingpolymers may be present in an aqueous emulsion.

Preferably, the one or more water insoluble film forming polymerscomprises of a terpolymer of vinyl acetate, mono-n-butyl maleate andisobornyl acrylate. Preferably, the terpolymer of vinyl acetate,mono-n-butyl maleate and isobornyl acrylate is dissolved in ethanol.

Preferably, the one or more water insoluble film forming polymerscomprises of a silicone-organic hybrid material of crotonic acid/vinylC₈₋₁₂ isoalkyl esters/VA/bis-vinyldimethicone crosspolymer. Preferably,the crotonic acid/vinyl C₈₋₁₂ isoalkyl esters/VA/bis-vinyldimethiconecrosspolymer is dissolved in ethanol.

Preferably, the one or more water insoluble film forming polymerscomprises of a biopolymer of shellac. Preferably, the shellac isdissolved in ethanol.

Preferably, the one or more water insoluble film forming polymerscomprises of at least two water insoluble film forming polymers selectedfrom the group consisting of trimethylsiloxysilicate, isododecane (and)acrylate/dimethicone copolymer, and acrylates/dimethicone copolymer(and) cyclopentasiloxane. Preferably, the at least two water insolublefilm forming polymers are dissolved in one or both of isododecane andisohexadecane.

Preferably, the one or more water insoluble film forming polymerscomprises of at least two water insoluble film forming polymers selectedfrom the group consisting of methyl dihydroabietate,trimethylsiloxysilicate, hydrogenated polycyclopentadiene (and)isododecane, acrylates/dimethicone copolymer (and) cyclopentasiloxane,and combinations thereof. Preferably, the at least two water insolublefilm forming polymers are dissolved in one or more solvents selectedfrom the group consisting of isododecane, isohexadecane, disiloxane anddiisopropyl adipate.

The sunscreen composition may further include one or more active orinactive cosmetic ingredients comprising of cosmetically acceptablecarriers; oils; sterols; amino acids; moisturizers; powders; colorants;pigments; dyes; pH adjusters; perfumes; essential oils; cosmetic activeingredients; vitamins; essential fatty acids; sphingolipids;self-tanning compounds; fillers; emulsifying agents; antioxidants;surfactants; additional film formers; chelating agents; gelling agents;thickeners; emollients; humectants; moisturizers; minerals; viscosityand/or rheology modifiers; keratolytics; retinoids; hormonal compounds;alpha-keto acids; anti-mycobacterial agents; anti-fungal agents;anti-microbials; anti-virals; analgesics; anti-allergenic agents; H1 orH2 antihistamines; anti-inflammatory agents; anti-irritants;anti-neoplastics; immune system boosting agents; immune systemsuppressing agents; anti-acne agents; anesthetics; antiseptics; insectrepellents; skin cooling compounds; skin protectants; skin penetrationenhancers; exfoliants; lubricants; fragrances; colorants; stainingagents; depigmenting agents; hypopigmenting agents; preservatives;stabilizers; pharmaceutical agents; photostabilizing agents; sphericalpowders; one or more fragrances; plant extracts; absorbents; salicylicacid; alpha and beta hydroxy acids; vitamins; retinol and itsderivatives; or any combination of the foregoing.

It is still yet another object of the invention to provide a sunscreencomposition comprising: one or more UVA sunscreen active agents; one ormore water insoluble film forming polymers comprising of monomers,copolymers, cross polymers and terpolymers of organo-silicone hybrids,biopolymers, acrylate, abietic acid derivatives, polyolefins, siliconeresins, vinyl acetates, maleates, alkyl esters, long chain and shortchain carboxylic acids, or combinations thereof; and one or moresolvents comprising C2-10 alcohol, ether, fatty acid, silicone fluid,ester, hydrocarbon, fluorinated hydrocarbon, wherein said one or morewater insoluble film forming polymers increase water resistance of saidone or more UVA sunscreen active agents such that retention of UVAPFvalues after water exposure, as determined by UVAPF values measuredbefore and after water exposure, is greater than at least 70%.Preferably, in one embodiment, the one or more water insoluble filmforming polymers is present in an amount of up to 6 wt. % and the one ormore solvents comprises ethanol. Preferably, in an alcohol-freeembodiment, the one or more water insoluble film forming polymers ispresent in an amount of up to 6 wt. % and the one or more solventscomprises isododecane, isohexadecane, disiloxane, diisopropyl adipate,or a combination thereof.

It is another object of the present invention to provide a sunscreencomposition comprising: one or more UVA sunscreen active agents; one ormore UVB sunscreen active agents; one or more water insoluble filmforming polymers, wherein the one or more water insoluble film formingpolymers increase water resistance of the one or more UVA sunscreenactive agents such that the level of retention of UVAPF values afterwater exposure, as determined by UVAPF values measured before and afterwater exposure, is greater than at least 60%.

It is yet another object of the present invention to provide a consumerpackaged product comprising a sunscreen composition as disclosed herein.

It is still yet another object of the present invention to provide amethod of absorbing ultraviolet radiation on a keratinous substratecomprising applying a sunscreen composition according to the embodimentsdisclosed herein to a keratinous substrate and subjecting the keratinoussubstrate to ultraviolet radiation.

BRIEF DESCRIPTION OF THE DRAWINGS

The features of the disclosure believed to be novel and the elementscharacteristic of the invention are set forth with particularity in theappended claims. The figures are for illustration purposes only and arenot drawn to scale. The disclosure itself, however, both as toorganization and method of operation, can best be understood byreference to the description of the preferred embodiment(s) whichfollows, taken in conjunction with the accompanying drawings in which:

FIG. 1 is a schematic showing that upon exposure to water over time, thelevel of protection from UV radiation decreases at a faster rate for theUVA active agents in comparison with UVB active agents.

DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

The embodiments of the present invention can comprise, consist of, andconsist essentially of the features and/or steps described herein, aswell as any of the additional or optional ingredients, components,steps, or limitations described herein or would otherwise be appreciatedby one of skill in the art. It is to be understood that allconcentrations disclosed herein are by weight percent (wt. %.) based ona total weight of the composition unless otherwise indicated. Whereappropriate, the INCI (International Nomenclature of CosmeticIngredients) name of ingredients/components is used.

A wide variety of sunscreen compositions contain both UVA active agentsand UVB active agents. When these sunscreens are exposed to water it hasbeen found that the UVA active agents wash off faster than their UVBcounterparts. Some UVA active agents are water soluble such that uponexposure to water and/or sweat, they are washed away completely therebyexposing the user to harmful UVA rays. Upon exposure to water and/orsweat, the efficacy of both the UVB and UVA active agents in thesunscreen compositions is depleted, unless there is re-application ofthe sunscreen composition. It has further been found that over user weartime, the UVA active agents and their corresponding protection from UVAradiation are lost at a higher rate and amount as compared to the UVBactive agents therein. As such, using only the SPF as a measure of waterresistance is insufficient to measure the level of protection from UVAradiation.

Table I is a list of sunscreen UVB and UVA active agents and theircorresponding degrees of lipophilicity, measured as relative polarities(water (log P)).

TABLE I Relative Lipophilicity of Sunscreen Chemicals Based Upon TheirCalculated Partition Coefficients Between Octanol and Water Log P CTFAname Other names @25° C. Glyceryl PABA1,2,3-Propanetriol,1-(4-aminobenzoate) −0.02 Benzophenone-4Sulisobenzone −1.51 PABA p-Amino benzoic acid 0.74 Benzophenone-8Dioxybenzone 2.15 Cinoxate Ethoxyethyl methoxy cinnamate 2.55Benzophenone-3 Oxybenzone 2.63 Ethyl dihydroxypropyl PABAEthyl-4-bis(2-hydroxypropyl-aminobenzoate) 2.84 Amyl dimethyl PABA Amyldimethyl PABA 4.53 Butylmethoxy dibenzoylmethane Butylmethoxydibenzoylmethane 4.86 Menthyl anthranilate Menthyl-O-aminobenzoate 5.05Octyl salicylate 2-Ethylhexyl salicyalate 5.30 Homosalate Homomenthylsalicylate 5.61 Octyl methoxy cinnamate Ethylhexyl-p-methoxy cinnamate5.65 Octocrylene Octyl cyanodiphenylacrylate 5.69 Octyl dimethyl PABA2-Ethylhexyl-p-dimethyl aminobenzoate 6.08 (See J. Soc. Cosmetic Chem.,38, 209-221, Table V (July/August 1987).)The data is listed in decreasing order of polarity (i.e., increasing logP values), and shows that the lipophilicity of sunscreens increase fromwater soluble (log P<1) to oil-soluble (log P>1). The table shows UVAactive agents, e.g., avobenzone (butylmethoxy dibenzoylmethane), havinglower polarities than their counterpart UVB active agents, e.g.,octocrylene. Based on these polarities, UVA active agents tend to bemore water soluble than UVB active agents. For instance, the polaritiesbased on log P values show that avobenzone is more easily washed offthan octocrylene such that upon exposure to water over time, the levelof protection from UV radiation decreases at a faster rate for the UVAactive agents in comparison with UVB active agents as shown in theschematic of FIG. 1.

In accordance with the various embodiments of the invention, sunscreencompositions, products, and methods are provided that unexpectedlyincrease water resistance of UVA active agents. In one or moreembodiments, sunscreen compositions are provided having improved waterresistance with greater retention of both UVB active agents and UVAactive agents after exposure to water and/or sweat. The varioussunscreen compositions of the invention include at least one or morepolymer additives that synergistically affect the UVA active agentspresent in the compositions to unexpectedly retain a desirable level ofprotection against UVA radiation after exposure to water and/or sweat.

The present invention includes one or more polymeric additives incombination with various sunscreen UVB and UVA active agents to providea sunscreen composition that has enhanced water resistance, andpreferably enhanced water resistance of the UVA active agent, afterwater exposure. In one or more embodiments, the polymer additive is awater insoluble film forming polymer. The various water insoluble filmforming polymers suitable for use in the present invention provide theresultant sunscreen composition with preferably greater than 60%retention, more preferably greater than 70% retention, and mostpreferably greater than 80% retention of the UVAPF levels after waterexposure.

The sunscreen compositions of the invention may include varioussunscreen active agents. Suitable sunscreen actives that may be used insunscreen compositions of the invention include, but are not limited to,one or more of the following: p-aminobenzoic acid (PABA) and derivativesthereof; avobenzone (also known as butylmethoxy dibenzoylmethane);2,4-dihydroxybenzophenone; 2,2′,4,4′-tetrahydroxybenzophenone;oxybenzone; sulisobenzone; sulisobenzone sodium;2,2′-dihydroxy-4,4′-dimethoxybenzophenone;5-chloro-2-hydroxybenzophenone; dioxybenzone; sodium2,2′-dihydroxy-4,4′-dimethoxybenzophenone-5,5′-disulfonate;2-hydroxy-4-methoxy-4′-methyl-benzophenone; octabenzone; ethyldihydroxypropyl-p-aminobenzoate; glyceryl-p-aminobenzoate; homosalate;methyl anthranilate; octocrylene; octyl dimethyl-p-aminobenzoate;isoamyl-p-methoxycinnamate; octyl methoxycinnamate; octyl salicylate;triethanolamine salicylate; 3-(4-methylbenzylidene) camphor; enzacamene;phenylbenzimidazole sulfonic acid; methylene bis-benzotriazolyltetramethylbutyl phenol; 4-isopropyldibenzoylmethane; octisalate;bis-ethylhexyloxyphenol methoxyphenyl triazine;4-isopropyl-dibenzoylmethane; metal oxides such as zinc oxide ortitanium dioxide; terephthalylidene dicamphor sulfonic acid (also knownas ecamsule); drometrizole trisiloxane; diethylhexylbutamido triazone;ethylhexyl triazone; cinoxate; ensulizole; bis-disulizole disodium;diethylamino hydroxybenzoyl hexylbenzoate; or combinations thereof. Itshould be appreciated and understood that the present sunscreencompositions may include one or more other known ingredients suitablefor use in absorbing, scattering and/or deflecting UVA and UVB radiationon a keratinous substrate.

Preferred sunscreen active agents that absorb and provide protection inthe UVB spectrum include, but are not limited to, octocrylene;octinoxate; octisalate; homosalate; ensulizole; ethylhexyl triazone;enzacamene; amiloxate; diethylhexyl butamido triazine; benzylidenemalonate polysiloxane; padimate-O; trolamine salicylate; cinoxate; PABA;or combinations thereof.

Preferred sunscreen active agents that absorb and provide protection inthe UVA spectrum include, but are not limited to, avobenzone;terephthalylidene dicamphor sulfonic acid; bis-disulizole disodium;disodium phenyl dibenzimidazole tetrasulfonate; diethylaminohydroxybenzoyl hexylbenzoate; bis-diethylamino hydroxybenzoyl benzoate;bis-benzoxazolylphenyl ethylhexylamino triazine, or combinationsthereof.

Preferred sunscreen active agents that absorb and provide both broad UVAand UVB protection include, but are not limited to, oxybenzone;meradimate; titanium dioxide; zinc oxide; bis-octrizole; bemotrizinol;drometrizole trisiloxane; sulisobenzone; dioxybenzone, or combinationsthereof.

The various sunscreen active agents of the instant sunscreenformulations may be present in an amount of about 0.01 wt. % to about40.0 wt. %, based on a total weight of the sunscreen composition. Theindividual weight percentage amounts and types of sunscreen activeagents of the instant compositions will vary depending upon the desiredsun protection factor (SPF) and the UVA Protection Factor (UVAPF). Thehigher the SPF and UVAPF, the greater the total amount of sunscreenactive agents. The one or more sunscreen active agents may be present inan amount of about 3.0 wt. % to about 30.0 wt. % to achieve a SPF ofabout 15 to about 200 and more, based on a total weight of the sunscreencomposition. The one or more additional sunscreen agents may be presentin an amount of about 3.0 wt. % to about 25.0 wt. %, based on a totalweight of the sunscreen composition, for a lower SPF.

The sunscreen compositions further include at least one or more polymeradditives that enhance the water resistance of the sunscreen compositionand, in particular, the UVA active agents after exposure to water. Theone or more polymer additives have a synergistic effect on the sunscreenactive agents, particularly on the UVA active agents, enhancing thewater resistance during water activity or sweat. The one or more polymeradditives suitable for use in the invention provide high retention ratesof UVAPF values of greater than at least 60%, more preferably greaterthan at least 70%, and most preferably greater than at least 80%, afterwater exposure as determined by UVAPF values measured before and afterwater exposure.

The one or more polymer additives comprise water insoluble film formingpolymers. The water insoluble film forming polymers comprise, but arenot limited to, monomers, copolymers, cross polymers and/or terpolymersof organo-silicone hybrids, silicone resins, biopolymers, acrylates,abietic acid derivatives, polyolefins, vinyl acetates, maleates, alkylesters, long chain and short chain carboxylic acids, and combinationsthereof.

Exemplary of the water insoluble film forming polymers as a terpolymeris vinyl acetate (VA)/butyl maleate/isobornyl acrylate copolymercommercially available as ADVANTAGE™ Plus from Ashland Inc., Covington,Ky., as a 50% ethanolic solution. Exemplary of an organo-silicone hybridis ethanol (and) crotonic acid/vinyl C₈₋₁₂ isoalkylesters/VA/bis-vinyldimethicone crosspolymer commercially available asBELSIL® P1101 available from Wacker Chemie AG, Laramie, Wyo. Exemplaryof biopolymers is shellac commercially available as POLY-SOLEIL® fromMantrose-Haeuser Co., Inc., Westport, Conn. Exemplary acrylatecopolymers useful as water insoluble film forming polymers areisododecane (and) acrylate/dimethicone copolymer such as, KP 550, oracrylates/dimethicone copolymer (and) cyclopentasiloxane such as KP 545,both commercially available from Shin-Etsu Chemical Co., Ltd., Japan. Anexemplary abietic acid derivative is methyl dihydroabietate, such asMERISTANT® 101L commercially available from Essential Ingredients,Lawrenceville, Ga. Exemplary of a polyolefinic water insoluble filmforming polymer useful in the present invention is hydrogenatedpolycyclopentadiene (and) isododecane commercially available asKOBOGUARD® 5400 IDD available from Kobo Products, Inc., SouthPlainfield, N.J., sold as an isododecane solution. Exemplary of asilicone resin useful in the present invention is MQ Solid Resincommercially available from Dow Corning Corporation, Midland, Mich.

The water insoluble film forming polymers may be provided in amountsranging from 0.2 wt. % to about 15 wt. %, of the total weight of thesunscreen composition, preferably from about 1.0 wt. % to about 10 wt.%, and most preferably from about 1.5 wt. % to about 6.0 wt. % (of thetotal weight of the sunscreen composition). While the water insolublefilm forming polymers are known film formers, it is unexpected that theaddition of these polymeric additives to a sunscreen composition wouldenhance water resistance of both UVB and UVA active agents, andsignificantly maximize the water resistance of UVA active agents suchthat the level of retention of the UVAPF values after water exposure isgreater than at least 60%.

In preparing the sunscreen compositions of the present invention, thewater insoluble film forming polymers are provided in solution in onephase, and added to another phase containing the sunscreen activeagents. These water insoluble film forming polymers are preferablydissolved or suspended in a non-aqueous solvent although sunscreencompositions utilizing emulsions involving aqueous phases are alsocontemplated herein. Such non-aqueous solvents include, but are notlimited to, C₂ to C₁₀ alcohols, ethers, fatty acids, silicone fluids,esters, hydrocarbons, and fluorinated hydrocarbons. Some of thecommercially available water insoluble film forming polymers are sold asa solution in a non-aqueous solvent, for example, ADVANTAGE Plus,KOBOGUARD, and others disclosed herein.

In some embodiments, the sunscreen composition includes sunscreen activeagents, and a synergistic combination of a water insoluble film formingpolymer comprising 3 wt. % VA/butyl maleate/isobornyl acrylate copolymerand the solvent is ethanol.

In some embodiments, the sunscreen composition includes sunscreen activeagents, and a synergistic combination of a water insoluble film formingpolymer comprising 3 wt. % crotonic acid/vinyl C₈₋₁₂ isoalkylesters/VA/bis-vinyldimethicone crosspolymer and the solvent is ethanol.

In some embodiments, the sunscreen composition includes sunscreen activeagents, and a synergistic combination of a water insoluble film formingpolymer comprising 1.5 wt. % shellac and the solvent is ethanol.

In some embodiments, the sunscreen composition includes sunscreen activeagents, and a synergistic combination of a water insoluble film formingpolymer comprising 3 wt. % trimethylsiloxysilicate, 3 wt. % isododecane(and) acrylate/dimethicone copolymer and the solvents are isododecaneand isohexadecane.

In some embodiments, the sunscreen composition includes sunscreen activeagents, and a synergistic combination of a water insoluble film formingpolymer comprising 0.5 wt. % trimethylsiloxysilicate, 0.2 wt. %acrylate/dimethicone copolymer (and) cyclopentasiloxane and the solventis isododecane.

In some embodiments, the sunscreen composition includes sunscreen activeagents, and a synergistic combination of a water insoluble film formingpolymer comprising 3 wt. % trimethylsiloxysilicate, 3 wt. %acrylate/dimethicone copolymer (and) cyclopentasiloxane and the solventsare isododecane and isohexadecane.

In some embodiments, the sunscreen composition includes sunscreen activeagents, and a synergistic combination of a water insoluble film formingpolymer comprising 3 wt. % trimethylsiloxysilicate, 3 wt. %acrylate/dimethicone copolymer (and) cyclopentasiloxane and the solventsare isododecane, isohexadecane, and disiloxane.

In some embodiments, the sunscreen composition includes sunscreen activeagents, and a synergistic combination of a water insoluble film formingpolymer comprising 2 wt. % trimethylsiloxysilicate, 1 wt. % methyldihydroabietate and the solvents are isododecane, isohexadecane, anddisiloxane.

In some embodiments, the sunscreen composition includes sunscreen activeagents, and a synergistic combination of a water insoluble film formingpolymer comprising 2 wt. % trimethylsiloxysilicate, 1 wt. % methyldihydroabietate and the solvents are isododecane, diisopropyl adipate,and disiloxane

In some embodiments, the sunscreen composition includes sunscreen activeagents, and a synergistic combination of a water insoluble film formingpolymer comprising 2 wt. % polycyclopentadiene (and) isododecane and thesolvents further include isohexadecane and disiloxane.

In some embodiments, the sunscreen composition includes sunscreen activeagents, and a synergistic combination of a water insoluble film formingpolymer comprising 2 wt. % methyl dihydroabietate and the solvents areisododecane, isohexadecane and disiloxane.

In some embodiments, the sunscreen composition includes sunscreen activeagents, and a synergistic combination of a water insoluble film formingpolymer comprising 4 wt. % polycyclopentadiene (and) isododecane and thesolvents further include isohexadecane and disiloxane.

In some embodiments, the sunscreen composition includes sunscreen activeagents, and a synergistic combination of a water insoluble film formingpolymer comprising 4 wt. % methyl dihydroabietate and the solvents areisododecane, isohexadecane and disiloxane.

While the invention has been described in relation to two phases of theresultant sunscreen compositions (i.e., Phase A and Phase B), it shouldbe appreciated and understood that multiple phases of compositions maybe prepared and ultimately mixed to provide the various sunscreencompositions of the invention having improved UVA water resistance. Inaccordance with one or more embodiments, the ingredients or constituentsof a first phase containing the sunscreen active agents, with or withoutother cosmetic ingredients, are provided into a vessel and mixed undertemperatures of about 70° C. to 75° C. until a uniform or clear solutionis rendered. This solution is cooled to a temperature of about 30° C.with continuous mixing. In a separate vessel, the water-insolublepolymeric additives are dissolved in a solvent and mixed at atemperature of about 30° C. until a homogeneous water insoluble polymeradditive second phase solution is rendered. The first and second phasesmay then be mixed together until a homogenous solution is obtained.Optionally, preservatives, such as phenoxyethanol as an example only,may be added to the sunscreen formulation, and the composition cooled,preferably to room temperature. Adjustments to the pH of the finalsunscreen composition may also be made at this time.

The sunscreen composition may further include one or more active orinactive cosmetic ingredients, such as, but not limited to, cosmeticallyacceptable carriers; oils; sterols; amino acids; moisturizers; powders;colorants (including pigments and/or dyes); pH adjusters; perfumes;essential oils; cosmetic active ingredients; vitamins; essential fattyacids; sphingolipids; self-tanning compounds such as dihydroxyacetone(DHA) and erythruloses; fillers; emulsifying agents; antioxidants;surfactants; additional film formers; chelating agents; gelling agents;thickeners; emollients; humectants; moisturizers; minerals; viscosityand/or rheology modifiers; keratolytics; retinoids; hormonal compounds;alpha-keto acids; anti-mycobacterial agents; anti-fungal agents;anti-microbials; anti-virals; analgesics; anti-allergenic agents; H1 orH2 antihistamines; anti-inflammatory agents; anti-irritants;anti-neoplastics; immune system boosting agents; immune systemsuppressing agents; anti-acne agents; anesthetics; antiseptics; insectrepellents; skin cooling compounds; skin protectants; skin penetrationenhancers; exfoliants; lubricants; fragrances; colorants; stainingagents; depigmenting agents; hypopigmenting agents; preservatives;stabilizers; pharmaceutical agents; photostabilizing agents; sphericalpowders; one or more fragrances; plant extracts; absorbents; salicylicacid; alpha and beta hydroxy acids; vitamins including vitamins A, C,and E; retinol and its derivatives; or any combination of the foregoing.It should be appreciated and understood that this list is not limiting,and that various other active or inactive ingredients may be used in thepresent sunscreen formulations.

Testing was performed on the sunscreen compositions of the invention. Invitro water resistance testing was performed on compositions of theinvention and the results analyzed using both high performance liquidchromatography (HPLC) and spectroscopic analysis, as well as in vivowater resistance using the methodology disclosed in the 2011 FDA FinalRule for Water Resistance to show the improved water resistance of theinventive compositions. In the spectroscopic analysis, absorbanceretention rates across both the UVB and UVA regions were obtained usingan ultraviolet spectrophotometer (Ultraviolet Transmittance AnalyzerModel UV-2000 available from Labsphere Inc., North Sutton, N.H.) andpresented in the below tables. In the spectroscopic analysis, an amountof the sunscreen compositions was uniformly applied to VITRO-SKIN®,commercially available from IMS, Inc., Portland, Me., by finger with apre-saturated finger cot. The coated plate was air-dried (e.g., forabout 15 minutes) and then placed inside the ultravioletspectrophotometer. Spectral absorbance measurements were taken at fourrandomly selected points. The readings were recorded by thespectrophotometer and the calculation of the SPF value was made based onthe following equation:

${SPF}_{{in}\mspace{11mu} {vitro}} = \frac{\int_{\lambda = 290}^{\lambda = 400}{{E(\lambda)} \times {I(\lambda)} \times d\; \lambda}}{\int_{\lambda = 290}^{\lambda = 400}{{E(\lambda)} \times {I(\lambda)} \times 10^{- {A_{0}{(\lambda)}}} \times d\; \lambda}}$

with the use of built-in software: UV-2000 application Version 1.1.0.0,wherein E(λ) is the erythemal action spectrum, I(λ) is the spectralirradiance received from the UV source, and A₀(λ) is the meanmonochromatic absorbance of the test product layer before UV exposure,and dλ is the wavelength step (1 nm). Averages of the four readings areshown in the below tables as the percent of UVB absorbance retentionbased on the measured SPF before and after water exposure.

Based on the ultraviolet spectrophotometer analysis and readings, theUVAPF in vitro water resistance was measured, and UVA absorbanceretention percentage was obtained using measurements before waterimmersion and after water immersion in accordance with the 2011 FDAFinal Rule for Very Water Resistance (VWR) based on eighty minutes ofsubmersion. The UVA absorbance retention percentage was calculated basedon the following equation:

${{UVA}\mspace{14mu} {Absorbance}\mspace{14mu} {Retention}\mspace{14mu} \%} = {\frac{\left( {{UVA}\mspace{14mu} {Absorbance}} \right)_{VWR}}{\left( {{UVA}\mspace{14mu} {Absorbance}} \right)_{Static}} \times 100\%}$

Concentration of UV active agents on a substrate as determined by HPLCwas also performed on samples of the inventive compositions. Testsamples were applied in duplicate onto a substrate followed by waterimmersion of one substrate containing sample over one or more timedintervals. The test sample was extracted from both the immersedsubstrate and the un-immersed substrate and HPLC assay was conducted onthe diluent from each substrate. The difference in before and aftermeasurements provides the amount of each UV active agent lost due towater exposure. The in vitro HPLC sunscreen retention percentages of thefollowing active agents: octocrylene, avobenzone, octisalate andhomosalate, after water exposure are discussed below.

Sunscreen compositions of the invention were also tested using in vivomethods to show the enhanced retention rates of the UVB and UVA activeagents in the inventive compositions after water exposure. Table IIbelow shows in vivo water resistance retention percentages across boththe UVB and UVA spectrum for Examples 1 to 3. These in vivo waterresistance tests confirm that the water insoluble film forming polymerssuitable in the present invention provide enhanced water resistance ofthe sunscreen composition, and significantly maximized the waterresistance of UVA active agents wherein greater than at least 60%, morepreferably greater than at least 70%, and most preferably greater thanat least 80%, UVA active agents are retained on the substrate surfaceafter water exposure, or even after exposure to sweat.

Various sunscreen formulations in accordance with the invention are setforth in the following examples. It should be appreciated and understoodthat these formulations may be modified and/or added to with variousconstituents at different concentrations while still falling within thescope of the invention.

Examples

In all examples, the inventive compositions contained the followingsunscreen active agents: homosalate (10 wt. %), octocrylene (6 wt. %),octisalate (5 wt. %), avobenzone (3 wt. %); and the following cosmeticingredients: caprylyl glycol (0.70 wt. %), tocopheryl acetate (0.01 wt.%), and aloe barbadensis leaf extract (and) mineral oil (0.01 wt. %),all based on a total weight of the sunscreen composition.

Examples 1 to 3 are inventive anhydrous formulations wherein the waterinsoluble film forming polymers are dissolved in an alcohol. Theseexamples were formulated as aerosols. The first phase included the UVAand UVB components as well as the above mentioned cosmetic ingredients.The first phase constituents were provided into a beaker neat, heated toabout 70° C. to 75° C. with mixing until a clear solution was obtained.The solution was then allowed to cool to a temperature of about 30° C.with continuous mixing.

The second phase constituents included at least one of the followingwater insoluble film forming polymers: VA/butyl maleate/isobornylacrylate copolymer; crotonic acid/vinyl C₈₋₁₂ isoalkylesters/VA/bis-vinyldimethicone crosspolymer, or shellac. These waterinsoluble film forming polymers were combined with an alcohol solvent,in particular, ethanol. The water insoluble film forming polymer andalcohol solvent were provided into and mixed in a separate beaker at atemperature of about 30° C. until a homogeneous solution was obtained.The two phases were combined until a clear solution was obtained.

Referring to Table II below, different alcohol-based sunscreencompositions were tested for UVB and UVA retention rates. These resultsshow the enhanced UVB and UVA retention rates due to use of the waterinsoluble film forming polymer additives in one or more embodiments ofalcohol based sunscreen compositions of the invention.

TABLE II Alcohol Based Sunscreen Compositions Example 1 2 3 PolymericAdditive VA/butyl crotonic acid/ shellac{circumflex over ( )} maleate/vinyl C₈₋₁₂ isobornyl isoalkyl esters/VA/ acrylate bis-vinyldimethiconecopolymer* crosspolymer⁺    3 wt. %    3 wt. %  1.5 wt. % Ethanol 72.28wt. % 72.28 wt. % 73.78 wt. % in vitro Water Resistance Test Data by UVSpectrophotometer retention of UVB 61.81% 93.41% 119.37% absorbanceretention of UVA 47.09% 83.50% 118.37% absorbance in vivo WaterResistance Test Data retention of SPF 88.09% 89.94% 87.42% retention ofUVAPF 73.31% 86.36% 95.29% Sunscreen Active Agent Retention (HPLC)homosalate 72.59% 82.94% 92.01% octocrylene 84.52% 90.30% 94.19%octisalate 66.38% 82.06% 92.37% avobenzone 25.42% 66.81% 75.91%*commercially available as ADVANTAGE Plus ⁺commercially available asBELSIL P1101 {circumflex over ( )}commercially available as POLY-SOLEIL

The in vitro water resistance test results analyzed by UVspectrophotometer, and the in vivo water resistance test results ofExamples 1 to 3 are shown in Table II. While these results show thatselected water insoluble film forming polymers may show more retentionof UVB and UVA in one test method as compared to another, the unexpectedadvantage is that all three water insoluble film forming polymers showenhanced water resistance of both UVB and UVA active agents in one testmethod or the other, and importantly, a significant enhancement (e.g.,preferably at least 60% or greater retention) in water resistance of UVAactive agents not found in conventional sunscreen formulations. Forexample, while the in vitro water resistance data of Example 1 shows amodest retention of UVA absorbance, the in vivo test data shows asignificant retention of UVA absorbance that was not predicted by the invitro data. In vivo test results in Examples 2 and 3 show the retentionof UVAPF on par with SPF not found in conventional sunscreencompositions due to the addition of the water insoluble film formingpolymers.

HPLC results show the effects of the individual water insoluble filmforming polymers of Examples 1 to 3 on different UVB and UVA activeagents. Examples 2 and 3 show a broader spectrum coverage with enhancedwater resistance of different UVB and UVA active agents after waterexposure. For instance, the HPLC results show that Examples 2 and 3retain the UVA active avobenzone to a significantly greater extent ascompared to Example 1, which is most similar to commercially availablesunscreen compositions.

In other examples of the present invention, alcohol-free compositionswere made in accordance with the various embodiments of the invention.Examples 4 to 13 shown in Table III show different alcohol-freecompositions having the following sunscreen actives agents: 10%homosalate, 5% octisalate, 6% octocrylene, and 3% avobenzone, withavobenzone providing the bulk of protection against UVA radiation. Likethat of the alcohol based formulations, these compositions may also bemade using one or more phases, with a first phase including one or moreUVA and UVB active agents and other cosmetic active or inactiveingredients and a second phase containing one or more of the waterinsoluble film forming polymers. These examples may include one, two, orpossibly more, water insoluble film forming polymers dissolved in one ormore, preferably at least two, organic solvents to provide a waterinsoluble film forming polymers second phase that is combined with thesunscreen active agent phase to render the present sunscreenformulations having enhanced UVB and/or UVA water resistance.

TABLE III Alcohol-Free Sunscreen Formulations Example 4 5 6 7 8 Polymertrimethylsiloxysilicate^(λ) trimethylsiloxysilicatetrimethylsiloxysilicate trimethylsiloxysilicate trimethylsiloxysilicateAdditive #1 3 wt. % 0.5 wt. % 3 wt. % 3 wt. % 2 wt. % Polymerisododecane acrylate/ acrylate/ acrylate/ methyl Additive#2 (and)dimethicone dimethicone dimethicone dihydro acrylate/ copolymercopolymer copolymer abietate dimethicone (and) (and) (and) copolymer^(μ)cyclopenta- cyclopenta- cyclopenta- siloxane^(✓) siloxane siloxane 3 wt.% 0.2 wt. % 3 wt. % 3 wt. % 1 wt. % Solvent #1 49.3 wt. % IDD 74.6% IDD49.3 wt. % 20 wt. % IDD 20 wt. % IDD IDD Solvent #2 20 wt. % IHD — 20wt. % IHD 20 wt. % IHD 20 wt. % IHD Solvent #3 — — — 29.3 wt. % DS 32.3wt. % DS in vitro Water Resistance Test Results (UV Spectrophotometer)retention 94% 109% 94% 92% 92% of UVB absorbance retention 73% 104% 90%71% 77% of UVA absorbance Example 9 10 11 12 13 Polymertrimethylsiloxysilicate polycyclopentadiene methyl polycyclopentadienemethyl Additive (and) dihydro (and) dihydro #1 isododecane^(Δ)abietate^(¥) isododecane abietate 2 wt. % 2 wt. % 2 wt. % 4 wt. % 4 wt.% Polymer methyl — — — — Additive#2 dihydro abietate 1 wt. % — — — —Solvent #1 20 wt. % IDD 42 wt. % IDD 42 wt. % IDD 20 wt. % IDD 20 wt. %IDD Solvent #2 20 wt. % 19 wt. % IHD 19 wt. % IHD 20 wt. % IHD 20 wt. %DIPA IHD Solvent #3 32.3 wt. % DS 12.3 wt. % DS 12.3 wt. % 31.3 wt. % DS31.3 wt. % DS DS in vitro Water Resistance Test Results (UVSpectrophotometer) retention 82% 58% 38% 66% 51% of UVB absorbanceretention 64% 42% 19% 51% 39% of UVA absorbance IDD = isododecane; IHD =isohexadecane; DS = disiloxane; DIPA = diisopropyl adipate {circumflexover ( )}commercially available as MQ-1600 Solid Resin ^(Δ)commerciallyavailable as KOBOGUARD 5400 IDD ^(¥)commercially available as MERISTANT101 L ^(μ)commercially available as KP 550 ^(✓)commercially available asKP 545

In vitro water resistance tests were analyzed using a UVspectrophotometer on Examples 4 to 13 and presented in Table III above.These results show the retention percent of both the UVB absorbance andUVA absorbance of the sunscreen compositions of Examples 4 to 13. Eachof the exemplary sunscreen compositions in Examples 4 to 9 exhibit highretention rates of greater than at least 60%, more preferably greaterthan at least 70%, and most preferably greater than at least 80%, of theUVA and UVB absorbance after water exposure measured using the UVspectrophotometer. A synergistic effect of more than one water insolublefilm forming polymers with one or more solvents is also evident notingthe high retention of UVA active agents after water exposure.

Examples 7 to 9 include one or more water-insoluble film formingpolymers in combination with at least three different solvents to renderthe sunscreen compositions of the invention. Thus, one of ordinary skillin the art can appreciate that in some embodiments, more than twowater-insoluble film forming polymers may be combined with more, orless, than three different solvents. Examples 7 to 9 provide enhancedwater resistance of both the UVB and UVA active agents.

Examples 10 to 13 include one water-insoluble polymeric additive incombination with at least three different solvents. These resultsillustrate the preference in one or more embodiments of the invention inutilizing combinations of water-insoluble polymeric additives when usingcombinations of solvents.

Commercial sunscreen compositions were evaluated as shown in Table IIA.The UVA sunscreen active agents are shown to wash off the skin afterwater immersion at much higher rates than those found in the inventivecompositions disclosed herein.

TABLE IIA Comparative Data Example CT BB1 in vivo Water Resistance TestData retention of SPF 94% retention of UVAPF 48% Sunscreen Active AgentRetention (HPLC) UVB actives 75% UVA actives 58% CT = Coppertone ®Clearly Sheer SPF 50+ BB1 = Banana Boat Clear Spray SPF 50

It has been found that the various sunscreen compositions of the presentinvention are more robust after water exposure providing consumers withlasting UVA protection and UVB protection. The synergistic effects ofthe various water-insoluble film forming polymers (either singularly orin combinations of two or more) suitable for use in the invention withUVB and UVA sunscreen active agents provides increased water resistanceof such active agents when exposed to water and/or sweat. One of skillin the art will understand how to formulate the inventive sunscreencompositions into suitable consumer packaged products.

In accordance with the various embodiments, the inventive sunscreencompositions may be formulated as continuous aerosol sprays, such as thealcohol-based aerosol sprays in Examples 1 to 3, oil-in-water (O/W) orwater-in-oil (W/O) emulsions, anhydrous topical formulations, lotions,creams, sprays, etc., as show in Examples 4 to 13. It has unexpectedlybeen found that the water insoluble film forming polymers suitable foruse in the invention provide sunscreen compositions having improvedwater resistance of both UVB and UVA active agents, with significantwater resistance enhancement of the UVA active agents. UVA active agentsare retained on a keratinous substrate to at least 60% or greaterretention after exposure to water and/or sweat. As such, the sunscreencompositions of the invention decrease the loss of UVA active agents onthe skin, and thereby increase protection from UV radiation between 320nm and 400 nm wavelengths, after water wash, water immersion, swimming,sweating, and the like.

While the present invention has been particularly described, inconjunction with a specific preferred embodiment, it is evident thatmany alternatives, modifications and variations will be apparent tothose skilled in the art in light of the foregoing description. It istherefore contemplated that the appended claims will embrace any suchalternatives, modifications and variations as falling within the truescope and spirit of the present invention.

Thus, having described the invention, what is claimed is:

What is claimed is:
 1. A sunscreen composition comprising: one or moreUVA sunscreen active agents; one or more water insoluble film formingpolymers, wherein said one or more water insoluble film forming polymersincrease water resistance of said one or more UVA sunscreen activeagents such that retention of UVAPF values after water exposure, asdetermined by UVAPF values measured before and after water exposure, isgreater than at least 60%.
 2. The sunscreen composition of claim 1wherein said one or more water insoluble film forming polymers increasewater resistance of said one or more UVA sunscreen active agents suchthat the level of retention of UVAPF values after water exposure asdetermined by UVAPF values measures before and after water exposure isgreater than at least 70%.
 3. The sunscreen composition of claim 1wherein said one or more water insoluble film forming polymers increasewater resistance of said one or more UVA sunscreen active agents suchthat the level of retention of UVAPF values after water exposure asdetermined by UVAPF values measures before and after water exposure isgreater than at least 80%.
 4. The sunscreen composition of claim 1wherein said one or more UVA sunscreen active agents compriseavobenzone; terephthalylidene dicamphor sulfonic acid; bis-disulizoledisodium; disodium phenyl dibenzimidazole tetrasulfonate; diethylaminohydroxybenzoyl hexylbenzoate; bis-diethylamino hydroxybenzoyl benzoate;bis-benzoxazolylphenyl ethylhexylamino triazine, or combinationsthereof.
 5. The sunscreen composition of claim 1 further including oneor more UVB sunscreen active agents.
 6. The sunscreen composition ofclaim 5 wherein said one or more UVB sunscreen active agents compriseoctocrylene; octinoxate; octisalate; homosalate; ensulizole; ethylhexyltriazone; enzacamene; amiloxate; diethylhexyl butamido triazine;benzylidene malonate polysiloxane; padimate-O; trolamine salicylate;cinoxate; p-aminobenzoic acid and derivatives thereof; or combinationsthereof.
 7. The sunscreen composition of claim 1 wherein said sunscreencomposition includes one or more sunscreen active agents that absorbboth UVA and UVB radiation.
 8. The sunscreen composition of claim 7wherein said one or more sunscreen actives comprise oxybenzone;meradimate; titanium dioxide; zinc oxide; bis-octrizole; bemotrizinol;drometrizole trisiloxane; sulisobenzone; dioxybenzone; or combinationsthereof.
 9. The sunscreen composition of claim 1 wherein said one ormore water insoluble film forming polymers is present in an amount ofabout 0.2 wt. % to about 15 wt. %.
 10. The sunscreen composition ofclaim 1 wherein said one or more water insoluble film forming polymersis present in an amount of about 1.5 wt. % to about 6 wt. %.
 11. Thesunscreen composition of claim 1 wherein said one or more waterinsoluble film forming polymers comprise monomers, copolymers, crosspolymers and terpolymers of organo-silicone hybrids, biopolymers,acrylate, abietic acid derivatives, polyolefins, silicone resins, vinylacetates, maleates, alkyl esters, long chain and short chain carboxylicacids, or combinations thereof.
 12. The sunscreen composition of claim 1wherein said one or more water insoluble film forming polymers arepresent in a non-aqueous solvent.
 13. The sunscreen composition of claim12 wherein said non-aqueous solvent comprises an alcohol, ether, fattyacid, silicone fluid, ester, hydrocarbon, fluorinated hydrocarbon, orcombinations thereof.
 14. The sunscreen composition of claim 13 whereinsaid non-aqueous solvent comprises a C₂₋₁₀ alcohol.
 15. The sunscreencomposition of claim 13 wherein said non-aqueous solvent comprisesisododecane, isohexadecane, disiloxane, diisopropyl adipate, andcombinations thereof.
 16. The sunscreen composition of claim 1 whereinsaid one or more water insoluble film forming polymers are present in anaqueous emulsion.
 17. The sunscreen composition of claim 1 wherein saidone or more water insoluble film forming polymers comprise a terpolymerof vinyl acetate, mono-n-butyl maleate and isobornyl acrylate.
 18. Thesunscreen composition of claim 17 wherein said terpolymer of vinylacetate, mono-n-butyl maleate and isobornyl acrylate is dissolved inethanol.
 19. The sunscreen composition of claim 1 wherein said one ormore water insoluble film forming polymers comprise a silicone-organichybrid material of crotonic acid/vinyl C₈₋₁₂ isoalkylesters/VA/bis-vinyldimethicone crosspolymer.
 20. The sunscreencomposition of claim 19 wherein said crotonic acid/vinyl C₈₋₁₂ isoalkylesters/VA/bis-vinyldimethicone crosspolymer is dissolved in ethanol. 21.The sunscreen composition of claim 1 wherein said one or more waterinsoluble film forming polymers comprise a biopolymer of shellac. 22.The sunscreen composition of claim 21 wherein said biopolymer of shellacis dissolved in ethanol.
 23. The sunscreen composition of claim 1wherein said one or more water insoluble film forming polymers compriseat least two water insoluble film forming polymers selected from thegroup consisting of trimethylsiloxysilicate, isododecane (and)acrylate/dimethicone copolymer, and acrylates/dimethicone copolymer(and) cyclopentasiloxane.
 24. The sunscreen composition of claim 23wherein said at least two water insoluble film forming polymers aredissolved in one or both of isododecane and isohexadecane.
 25. Thesunscreen composition of claim 1 wherein said one or more waterinsoluble film forming polymers comprise at least two water insolublefilm forming polymers selected from the group consisting of methyldihydroabietate, trimethylsiloxysilicate, hydrogenatedpolycyclopentadiene (and) isododecane, acrylates/dimethicone copolymer(and) cyclopentasiloxane, and combinations thereof.
 26. The sunscreencomposition of claim 25 wherein said at least two water insoluble filmforming polymers are dissolved in one or more of solvents selected fromthe group consisting of isododecane, isohexadecane, disiloxane anddiisopropyl adipate.
 27. The sunscreen composition of claim 1 whereinsaid sunscreen composition includes sunscreen active agents comprisingsaid one or more UVA sunscreen active agents in combination with one ormore UVB sunscreen active agents, said sunscreen active agents presentin an amount of about 0.01 wt. % to about 40.0 wt. %, based on a totalweight of the sunscreen composition.
 28. The sunscreen composition ofclaim 27 wherein said sunscreen active agents are present in an amountof about 3.0 wt. % to about 30.0 wt. %.
 29. The sunscreen composition ofclaim 1 wherein said sunscreen composition further includes one or moreactive or inactive cosmetic ingredients.
 30. The sunscreen compositionof claim 29 wherein said one or more active or inactive cosmeticingredients comprise cosmetically acceptable carriers; oils; sterols;amino acids; moisturizers; powders; colorants; pigments; dyes; pHadjusters; perfumes; essential oils; cosmetic active ingredients;vitamins; essential fatty acids; sphingolipids; self-tanning compounds;fillers; emulsifying agents; antioxidants; surfactants; additional filmformers; chelating agents; gelling agents; thickeners; emollients;humectants; moisturizers; minerals; viscosity and/or rheology modifiers;keratolytics; retinoids; hormonal compounds; alpha-keto acids;anti-mycobacterial agents; anti-fungal agents; anti-microbials;anti-virals; analgesics; anti-allergenic agents; H1 or H2antihistamines; anti-inflammatory agents; anti-irritants;anti-neoplastics; immune system boosting agents; immune systemsuppressing agents; anti-acne agents; anesthetics; antiseptics; insectrepellents; skin cooling compounds; skin protectants; skin penetrationenhancers; exfoliants; lubricants; fragrances; colorants; stainingagents; depigmenting agents; hypopigmenting agents; preservatives;stabilizers; pharmaceutical agents; photostabilizing agents; sphericalpowders; one or more fragrances; plant extracts; absorbents; salicylicacid; alpha and beta hydroxy acids; vitamins; retinol and itsderivatives; or any combination of the foregoing.
 31. A sunscreencomposition comprising: one or more UVA sunscreen active agents; one ormore water insoluble film forming polymers comprising of monomers,copolymers, cross polymers and terpolymers of organo-silicone hybrids,biopolymers, acrylate, abietic acid derivatives, polyolefins, siliconeresins, vinyl acetates, maleates, alkyl esters, long chain and shortchain carboxylic acids, or combinations thereof; and one or moresolvents comprising C₂₋₁₀ alcohol, ether, fatty acid, silicone fluid,ester, hydrocarbon, fluorinated hydrocarbon, wherein said one or morewater insoluble film forming polymers increase water resistance of saidone or more UVA sunscreen active agents such that retention of UVAPFvalues after water exposure, as determined by UVAPF values measuredbefore and after water exposure, is greater than at least 70%.
 32. Thesunscreen composition of claim 31 wherein said one or more waterinsoluble film forming polymers is present in an amount of up to 10 wt.% and said one or more solvents comprises ethanol.
 33. The sunscreencomposition of claim 31 wherein said one or more water insoluble filmforming polymers is present in an amount of up to 6 wt. % and said oneor more solvents comprises ethanol.
 34. The sunscreen composition ofclaim 31 wherein said one or more water insoluble film forming polymersis present in an amount of up to 10 wt. % and said one or more solventscomprises isododecane, isohexadecane, disiloxane, diisopropyl adipate,or a combination thereof.
 35. The sunscreen composition of claim 31wherein said one or more water insoluble film forming polymers ispresent in an amount of up to 6 wt. % and said one or more solventscomprises isododecane, isohexadecane, disiloxane, diisopropyl adipate,or a combination thereof.
 36. A sunscreen composition comprising: one ormore UVA sunscreen active agents including avobenzone; one or more UVBsunscreen active agents; one or more water insoluble film formingpolymers present in an amount of up to about 10 wt. % based on a totalweight of said sunscreen composition, wherein said one or more waterinsoluble film forming polymers increase water resistance of said one ormore UVA sunscreen active agents such that retention of UVAPF valuesafter water exposure, as determined by UVAPF values measured before andafter water exposure, is greater than at least 60%.
 37. A consumerpackaged product comprising a sunscreen composition of claim
 1. 38. Aconsumer packaged product comprising a sunscreen composition of claim31.
 39. A consumer packaged product comprising a sunscreen compositionof claim
 32. 40. A consumer packaged product comprising a sunscreencomposition of claim 34 that is alcohol-free.
 41. A consumer packagedproduct comprising a sunscreen composition of claim
 36. 42. A method ofabsorbing ultraviolet radiation on a keratinous substrate comprisingapplying a sunscreen composition according to claim 1 to a keratinoussubstrate and subjecting the keratinous substrate to ultravioletradiation.
 43. A method of absorbing ultraviolet radiation on akeratinous substrate comprising applying a sunscreen compositionaccording to claim 31 to a keratinous substrate and subjecting thekeratinous substrate to ultraviolet radiation.
 44. A method of absorbingultraviolet radiation on a keratinous substrate comprising applying asunscreen composition according to claim 32 to a keratinous substrateand subjecting the keratinous substrate to ultraviolet radiation.
 45. Amethod of absorbing ultraviolet radiation on a keratinous substratecomprising applying an alcohol-free sunscreen composition according toclaim 34 to a keratinous substrate and subjecting the keratinoussubstrate to ultraviolet radiation.
 46. A method of absorbingultraviolet radiation on a keratinous substrate comprising applying asunscreen composition according to claim 36 to a keratinous substrateand subjecting the keratinous substrate to ultraviolet radiation.